CN101414679A - Composite material and preparation method thereof, and cathode and lithium battery - Google Patents
Composite material and preparation method thereof, and cathode and lithium battery Download PDFInfo
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- CN101414679A CN101414679A CNA2007101820188A CN200710182018A CN101414679A CN 101414679 A CN101414679 A CN 101414679A CN A2007101820188 A CNA2007101820188 A CN A2007101820188A CN 200710182018 A CN200710182018 A CN 200710182018A CN 101414679 A CN101414679 A CN 101414679A
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Abstract
The invention provides composite materials which contain carbon materials and amorphous carbon materials with lithium embedded/removed activity, wherein the carbon materials are carbon nano tubes equal to 100 weight portions of amorphous carbon materials with lithium embedded/removed activity, and the content of the carbon nano tubes is from 5 to 50 weight portions. The invention also provides a method for preparing the composite materials. The invention also provides a cathode containing the composite materials provided by the invention, and a lithium battery comprising the composite materials provided by the invention. The composite materials provided by the invention can simultaneously improve the specific capacity and the circulation performance of the obtained batteries.
Description
Technical field
The invention relates to a kind of composite material and preparation method thereof and negative pole and lithium battery.
Background technology
Present commercial lithium ion battery adopts lithium transition-metal oxide as positive electrode active materials and the graphite system as negative active core-shell material mostly, though the chemical property excellence of this class system, but it is lower itself to store up the lithium ability, particularly the theoretical capacity of graphite-like negative active core-shell material only is 372 MAH/grams, and so low capacity has been difficult to adapt to the miniaturization development of various portable electric appts and the electric automobile demand to big capacity, high power chemical power source at present.Therefore, studying at present a kind of new performance that the negative active core-shell material of height ratio capacity more improves lithium ion battery that has, meeting the need of market.
To studies show that of non-carbon negative active core-shell material, have the metal or alloy class material of many high storage lithium performances to use as negative active core-shell material, wherein silicon becomes the most attractive a kind of because of having embedding lithium specific capacity big (theoretical specific capacity can reach 4200 MAH/grams) and the low characteristics such as (less than 0.5 volts) of embedding lithium current potential.Yet, the conductivity of silicon materials itself is relatively poor, and in the process of removal lithium embedded, there is serious bulk effect, in the charge and discharge process of battery owing to volumetric expansion produces bigger mechanical stress, the cyclical stability of the battery that causes using silicon to do negative active core-shell material is poor, thereby has hindered the industrial applications of silicon.
For this reason, present many researchers are devoted to the modification and the optimal design of high lithium storage materials, and have obtained certain progress.The bulk effect problem that solves silicon materials has two kinds of methods usually: the one, and depositing silicon film on the collector of battery cathode, the advantage of this method is not need to add other component in the electrode, shortcoming is to be not suitable for large-scale production, and when the thickness of silicon thin film surpasses 1 micron, the diffusion length of lithium ion increases, and resistance increases.The 2nd, prepare siliceous composite material, modal is silicon/carbon composite.Though the affiliation that adds of carbon causes the specific capacity of composite material to descend to some extent, the specific capacity after reducing still is much higher than the specific capacity of carbon itself, therefore still can be used as the desirable substitute of carbon class negative active core-shell material.Silicon/carbon composite has two kinds of structures, and a kind of is " cake type " structure, is about to silicon grain and at first is dispersed in (mainly being pitch, resin etc.) in the organic precursor, organic substance is carried out high temperature carbonization again and handles, and obtains silicon/carbon composite.
CN1667855A discloses a kind of battery cathode active substance, and this negative electrode active material comprises silica-based compound and carbonaceous material, and this silica-based compound comprises Si oxide (SiO
x, wherein, x≤1.5) and at least a element, described element is selected from one or more among B, P, Li, Ge, Al, the V, and described carbonaceous material is selected from crystalline carbon and/or amorphous carbon, and the weight ratio of silica-based compound and carbonaceous material is 30:70-70:30.This preparation methods is, with silicon dioxide, Si and contain at least a compound in B compound, P-compound, Li compound, Ge compound, Al compound, the V compound, by mixture being heat-treated and quenching, prepare silica-based compound, then with silica-based compound, adopt chemical vapor deposition, with the indefinite-form carbon material coating thereon, prepare this negative electrode active material.But, since in this material the preparation of Si oxide by SiO
2Prepare with Si simple substance, agglomeration appears in the dispersion process easily, though and when silicone content is higher, the above-mentioned specific capacity that contains silicon composite is higher, but still have when discharging and recharging the problem that causes the cycle performance of battery difference because of the silicon volumetric expansion greatly when silicone content is higher, and silicone content is when low, though the cycle performance of battery increases, but the specific capacity of composite material is low, can not satisfy actual needs.
Summary of the invention
The objective of the invention is to improve simultaneously the shortcoming of the cycle performance of specific capacity and battery, provide a kind of specific capacity height and the composite material of the good cycle of the battery that obtains for the composite material that overcomes prior art.
The invention provides a kind of composite material, this material contains material with carbon element and has embedding/take off the non-material with carbon element of lithium activity, and wherein, described material with carbon element is a carbon nano-tube, with respect to 100 weight portions have an embedding/take off the non-material with carbon element of lithium activity, the content of described carbon nano-tube is the 5-50 weight portion.
The present invention also provides a kind of preparation method of composite material, wherein, this method comprises carries out ball milling with non-material with carbon element and carbon nano-tube with embedding/take off lithium activity under inert gas atmosphere or vacuum condition, dry then, with respect to 100 weight portions have an embedding/take off the non-material with carbon element of lithium activity, the consumption of described carbon nano-tube is the 5-50 weight portion.
The present invention also provides a kind of negative pole, and this negative pole comprises collector and the negative material that loads on this collector, and wherein, described negative material contains composite material provided by the invention.
The present invention also provides a kind of lithium battery, and this battery comprises pole piece and electrolyte, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, and wherein, described negative pole is a negative pole provided by the invention
In the composite material provided by the invention, described material with carbon element is a carbon nano-tube, carbon nano-tube has excellent toughness, even also can be under the content situation seldom of carbon nano-tube in composite material embedding/when taking off lithium, can play a kind of effect of buffering, make the battery that contains this composite material can not reduce the cycle performance of battery because of the expansion of composite material volume; Make simultaneously and can contain the more negative material with height ratio capacity in the composite material, in addition, carbon nano-tube also has storage lithium activity, can provide extra specific capacity for composite material, thereby can improve the specific capacity of composite material.
Embodiment
The invention provides a kind of composite material, this material contains material with carbon element and has embedding/take off the non-material with carbon element of lithium activity, and wherein, described material with carbon element is a carbon nano-tube, with respect to 100 weight portions have an embedding/take off the non-material with carbon element of lithium activity, the content of described carbon nano-tube is the 5-50 weight portion.
According to the present invention, although a spot of carbon nano-tube can realize purpose of the present invention, under the preferable case, have embedding/take off the non-material with carbon element of lithium activity with respect to 100 weight portions described, the content of described carbon nano-tube is the 10-30 weight portion.
Among the present invention, the size of described carbon nano-tube is had no particular limits, under the preferable case, the average tube diameter of described carbon nano-tube is the 10-100 nanometer, and length is the 1-30 micron; More preferably, average tube diameter is the 20-40 nanometer, and length is the 5-15 micron.The carbon nano-tube that use has above-mentioned average tube diameter and length can guarantee to form between the carbon nano-tube better conductive network, thereby further improve the conductivity of this composite material, and, the dispersiveness of carbon nano-tube in water with above-mentioned average tube diameter and length is better, when the preparation anode sizing agent, be not easy to reunite, and have an imbibition ability preferably, lower resistivity.Carbon nano-tube with above-mentioned size can be commercially available, for example, and the carbon nano-tube that Yantai Jialong Nanometer Industry Co., Ltd. produces.
Among the present invention, described non-material with carbon element with embedding/take off lithium activity can for various routines be used to prepare negative active core-shell material have embedding/take off a non-material with carbon element of lithium activity; It under the preferable case elemental silicon; Si oxide SiO
x, 0＜x≤1.5 wherein; Cobaltosic oxide; Di-iron trioxide; In tin oxide and the stannous oxide one or more; More preferably elemental silicon and/or Si oxide SiO
x, 0＜x≤1.5 wherein.
According to the present invention, the average grain diameter of the particle of described non-material with carbon element with embedding/take off lithium activity can in very large range change; Under the preferable case, described non-material with carbon element with embedding/take off lithium activity is a nanoscale, this is to increase and can be cushioned by the elasticity of carbon nano-tube in order to make by described particle with non-material with carbon element of embedding/take off lithium activity the volume that produces that expands, and has embedding/take off the mechanical stress that the particle of the non-material with carbon element of lithium activity produces because of volumetric expansion in charge and discharge process thereby alleviate.Described particle with embedding/take off non-material with carbon element of lithium activity can be the nanometer particle of all size and shape.For example, can be that mean particle diameter is 5-300 nanometer, the particle of 10-200 nanometer more preferably.Purity to the particle of component with embedding/take off lithium activity does not have special requirement, can be technical pure, analyze pure silicon particle or HIGH-PURITY SILICON particle.
The present invention also provides a kind of preparation method of composite material, wherein, this method comprises carries out ball milling with non-material with carbon element and carbon nano-tube with embedding/take off lithium activity under inert gas atmosphere or vacuum condition, dry then, with respect to 100 weight portions have an embedding/take off the non-material with carbon element of lithium activity, the consumption of described carbon nano-tube is the 5-50 weight portion.
According to the present invention, although a spot of carbon nano-tube can realize purpose of the present invention, under the preferable case, with respect to 100 weight portions have an embedding/take off the non-material with carbon element of lithium activity, the consumption of described carbon nano-tube is the 10-30 weight portion.
Among the present invention, the size of described carbon nano-tube is had no particular limits, under the preferable case, the average tube diameter of described carbon nano-tube is the 10-100 nanometer, and length is the 1-30 micron; More preferably, average tube diameter is the 20-40 nanometer, and length is the 5-15 micron.The carbon nano-tube that use has above-mentioned diameter and length can guarantee to form between the carbon nano-tube better conductive network, thereby further improve the conductivity of this composite material, and, the dispersiveness of carbon nano-tube in water with above-mentioned diameter and length is better, when the preparation anode sizing agent, be not easy to reunite, and have an imbibition ability preferably, lower resistivity.Carbon nano-tube with above-mentioned size can be commercially available, for example, and the carbon nano-tube that Yantai Jialong Nanometer Industry Co., Ltd. produces.
Among the present invention, described non-material with carbon element with embedding/take off lithium activity can for various routines be used to prepare negative active core-shell material have embedding/take off a non-material with carbon element of lithium activity; It under the preferable case elemental silicon; Si oxide SiO
x, 0＜x≤1.5 wherein; Cobaltosic oxide; Di-iron trioxide; In tin oxide and the stannous oxide one or more; More preferably elemental silicon and/or Si oxide SiO
x, 0＜x≤1.5 wherein.
According to the present invention, the average grain diameter of the particle of described non-material with carbon element with embedding/take off lithium activity can in very large range change; Under the preferable case, described non-material with carbon element with embedding/take off lithium activity is a nanoscale, this is to increase and can be cushioned by the elasticity of carbon nano-tube in order to make by described particle with non-material with carbon element of embedding/take off lithium activity the volume that produces that expands, and has embedding/take off the mechanical stress that the particle of the non-material with carbon element of lithium activity produces because of volumetric expansion in charge and discharge process thereby alleviate.Described particle with embedding/take off non-material with carbon element of lithium activity can be the nanometer particle of all size and shape.For example, can be that mean particle diameter is 5-300 nanometer, the nanometer particle of 10-200 nanometer more preferably.Purity to the particle of component with embedding/take off lithium activity does not have special requirement, can be technical pure, analyze pure silicon particle or HIGH-PURITY SILICON particle.
Among the present invention, the condition of described ball milling is had no particular limits, be well known to those skilled in the art, as long as component and the carbon nano-tube with embedding/take off lithium activity can be mixed.
In order to prevent the oxidation when the ball milling of negative material particle, described ball milling carries out under inert gas atmosphere or vacuum environment.Wherein, described inert gas can be one or more in group 0 element gas, nitrogen and the carbon dioxide.The pressure of described vacuum environment is 1 * 10
-2Below the handkerchief.
According to the present invention, can mix more uniformly with component in order to make carbon nano-tube with embedding/take off lithium activity, under the preferable case, described carbon nano-tube is also carried out acidification before ball milling, the method of described acidification comprise with carbon nano-tube with acid contact, described acid is nitric acid and/or sulfuric acid, the time of contact is 5-15 hour, be preferably 8-12 hour, the temperature of contact is 50-90 ℃.The purpose of described acidification is activated carbon nano-tube, the port of carbon nano-tube is opened, thereby make more even that carbon nano-tube mixes with the component with embedding/take off lithium activity, can better alleviate and have embedding/take off the mechanical stress that the particle of the component of lithium activity produces because of volumetric expansion in charge and discharge process.
The present invention also provides a kind of negative pole, and this negative pole comprises collector and the negative material that loads on this collector, and wherein, described negative material contains composite material provided by the invention.Because the present invention only relates to improvement to composite material, the preparation method of anticathode and the composition of negative pole are not particularly limited, for the preparation method of this area routine with form and get final product.For example, will contain and the invention provides to such an extent that the slurry of composite material and adhesive loads on the single or double of collector and oven dry, and cut into required size and can obtain negative pole of the present invention.Described collector can adopt all available negative current collectors known in the art, and the present invention has no particular limits it, for example can be the punched copper tape that red copper or other copper alloy make through punching press.The surface of preferred described punched copper tape also is coated with one deck tin or ashbury metal.
The present invention also provides a kind of lithium battery, and this battery comprises pole piece and electrolyte, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, and wherein, described negative pole is a negative pole provided by the invention.
Lithium battery provided by the invention has no particular limits described positive pole, membrane layer and electrolyte, can use all types of positive poles that can use in lithium battery, corresponding membrane layer and electrolyte.For example, anodal consisting of is conventionally known to one of skill in the art, and in general, positive pole comprises collector body and coating and/or is filled in positive electrode on the collector body.Positive electrode collector can be the collector body of being made by any electric conducting material that shows inertia in the lithium-ion electric pool environment of routine, as being aluminium foil, stainless steel foil or nickel foil, shape can be mesh-like or paper tinsel shape, uses aluminium foil as positive electrode collector in specific embodiments of the present invention.Described positive electrode is conventionally known to one of skill in the art, it comprises positive active material, anodal conductive agent and anodal adhesive, described positive active material can be selected from the positive active material of lithium rechargeable battery routine, as a kind of or its mixture: the Li in the following material
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0).Described conductive agent can be the anodal conductive agent of this area routine, such as the ketjen carbon black, acetylene black, furnace black, carbon fiber VGCF, one or more in nano-graphite, graphite and the electrically conductive graphite are benchmark with the positive active material, the content of described anodal conductive agent is 0.01-20 weight %, is preferably 0.5-10 weight %.Described anodal adhesive can adopt the adhesive identical with negative pole, the kind of described anodal adhesive and content are conventionally known to one of skill in the art, for example can be selected from polyvinyl alcohol, polytetrafluoroethylene, polyvinylidene fluoride, CMC and the butadiene-styrene rubber one or more.In general, according to the difference of used anodal adhesive kind, be benchmark with the positive active material, the content of described anodal adhesive is 0.5-8 weight %, is preferably 1-5 weight %.
The preparation method of described positive pole can adopt conventional preparation method.For example, the slurry of described positive active material, anodal conductive agent and anodal adhesive and solvent preparation is applied and/or is filled on the described collector body, drying, calendering can obtain described positive pole.The solvent that is used to prepare anode sizing agent of the present invention can be selected from conventional solvent, as being selected from N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols one or more.The consumption of described solvent can make described slurry have viscosity and flowability, can be coated on the described collector body to get final product.In general be benchmark with the positive active material, the content of described solvent is 30-90 weight %, is preferably 45-85 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.
Described barrier film has electrical insulation capability and liquid retainability energy, is arranged between positive pole and the negative pole, and is sealed in the battery case with positive pole, negative pole and electrolyte.Described barrier film can be the general various barrier films in this area, such as by nonwoven fabrics, the synthetic resin microporous barrier of those skilled in the art at the various production trades mark of known each manufacturer production, the preferred synthetic resin microporous barrier that adopts, be excellent with polyolefin microporous film again wherein, as in polyethene microporous membrane, microporous polypropylene membrane and the polyethylene polypropylene composite micro porous film one or more, what adopt in specific embodiments of the present invention is polyethylene, polypropylene composite diaphragm paper.
Described electrolyte is this area electrolyte commonly used, as the mixed solution of electrolyte lithium salt and nonaqueous solvents.Electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In the described electrolyte, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
The following examples will the present invention is described further.
Embodiment 1
This embodiment is used to illustrate composite material provided by the invention and preparation method thereof.
Carbon nano-tube (Yantai Jialong Nanometer Industry Co., Ltd. with 8 weight portions, average tube diameter is 15 nanometers, 25 microns of length) (English reaches new material Co., Ltd with the SiO of 100 weight portions, mean particle diameter is 300 nanometers) with Ar gas as the condition of protective atmosphere under in planetary ball mill (ND7-2L type Nanda Tianzun Electronics Co., Ltd., Nanjing), be to carry out ball milling under the condition of 250rpm at rotating speed, the temperature of ball milling is a room temperature, and the ball milling time is 2 hours, makes solvent with absolute ethyl alcohol; Mixture behind the ball milling is dry under 80 ℃ of vacuum conditions, obtain composite material S1.
Comparative Examples 1
Method according to embodiment 1 prepares composite material, and different is that adding acetylene black place of carbon nanotubes obtains reference composite material CS1.
Embodiment 2
This embodiment is used to illustrate composite material provided by the invention and preparation method thereof.
Carbon nano-tube (Yantai Jialong Nanometer Industry Co., Ltd. with 40 weight portions, average tube diameter is 80 nanometers, 4 microns of length) with the nano-silicon (particle diameter is 8 nanometers) of 100 weight portions with Ar gas as the condition of protective atmosphere under in planetary ball mill (ND7-2L type Nanda Tianzun Electronics Co., Ltd., Nanjing), be to carry out ball milling under the condition of 250rpm at rotating speed, the temperature of ball milling is a room temperature, the ball milling time is 2 hours, is solvent with the absolute ethyl alcohol; Mixture behind the ball milling is dry under 80 ℃ of vacuum conditions, obtain composite material S2.
Embodiment 3
This embodiment is used to illustrate composite material provided by the invention and preparation method thereof.
Carbon nano-tube (Yantai Jialong Nanometer Industry Co., Ltd. with 50 weight portions, average tube diameter is 90 nanometers, 20 microns of length) with the cobaltosic oxide (particle diameter is 100 nanometers) of the nano-silicon (particle diameter is 250 nanometers) of 80 weight portions and 20 weight portions with Ar gas as the condition of protective atmosphere under in planetary ball mill (ND7-2L type Nanda Tianzun Electronics Co., Ltd., Nanjing), be to carry out ball milling under the condition of 250rpm at rotating speed, the temperature of ball milling is a room temperature, the ball milling time is 2 hours, is solvent with the absolute ethyl alcohol; Mixture behind the ball milling is dry under 80 ℃ of vacuum conditions, obtain composite material S3.
Embodiment 4
This embodiment is used to illustrate composite material provided by the invention and preparation method thereof.
Carbon nano-tube (Yantai Jialong Nanometer Industry Co., Ltd. with 30 weight portions, average tube diameter is 40 nanometers, 10 microns of length) with the di-iron trioxide of the nano-silicon (particle diameter is 8 nanometers) of 75 weight portions and 25 weight portions (particle diameter is 200 nanometers) with Ar gas as the condition of protective atmosphere under in planetary ball mill (ND7-2L type Nanda Tianzun Electronics Co., Ltd., Nanjing), be to carry out ball milling under the condition of 250rpm at rotating speed, the temperature of ball milling is a room temperature, the ball milling time is 2 hours, is solvent with the absolute ethyl alcohol; Mixture behind the ball milling is dry under 80 ℃ of vacuum conditions, obtain composite material S4.
Embodiment 5
This embodiment is used to illustrate composite material provided by the invention and preparation method thereof.
With carbon nano-tube (Yantai Jialong Nanometer Industry Co., Ltd., average tube diameter is 20 nanometers, 15 microns of length) acidification 10 hours in 60 ℃ the concentrated sulfuric acid, use washed with de-ionized water, up to the pH=7 of filtrate, dry down at 120 ℃ then.
(English reaches new material Co., Ltd with the SiO of carbon nano-tube after the acidification of 10 weight portions and 80 weight portions, mean particle diameter is 100 nanometers) and the tin oxide (particle diameter is 50 nanometers) of 20 weight portions with Ar gas as the condition of protective atmosphere under in planetary ball mill (ND7-2L type Nanda Tianzun Electronics Co., Ltd., Nanjing), be to carry out ball milling under the condition of 250rpm at rotating speed, the temperature of ball milling is a room temperature, and the ball milling time is 2 hours; Mixture behind the ball milling is dry under 80 ℃ of vacuum conditions, obtain composite material S5.
Embodiment 6
This embodiment is used to illustrate composite material provided by the invention and preparation method thereof.
With carbon nano-tube (Yantai Jialong Nanometer Industry Co., Ltd., average tube diameter is 30 nanometers, 5 microns of length) acidification 12 hours in 90 ℃ red fuming nitric acid (RFNA), use washed with de-ionized water respectively, up to the pH=7 of filtrate, dry down at 120 ℃ then.
With the di-iron trioxide (particle diameter is 150 nanometers) of the cobaltosic oxide (particle diameter is 50 nanometers) of carbon nano-tube after the acidification of 30 weight portions and 50 weight portions and 50 weight portions with Ar gas as the condition of protective atmosphere under in planetary ball mill (ND7-2L type Nanda Tianzun Electronics Co., Ltd., Nanjing), be to carry out ball milling under the condition of 250rpm at rotating speed, the temperature of ball milling is a room temperature, the ball milling time is 2 hours, and acetone is made solvent; Mixture behind the ball milling is dry under 80 ℃ of vacuum conditions, obtain composite material S6.
Embodiment 7
This embodiment is used to illustrate the chemical property of siliceous composite sample provided by the invention.
1, electrochemical specific capacity
Test the electrochemical specific capacity of the composite sample S1 that makes by the foregoing description 1 according to following step:
With thickness is that 0.06 millimeter, diameter are that 16 millimeters, weight are that the metal lithium sheet of 0.0064 gram is a negative electrode active material, is barrier film with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolyte, is positive electrode with the composite material S1 that made by the foregoing description 1 and Kynoar with the mixture (0.125 gram) of weight ratio 80:20, makes 2016 type button cells.
According to following step measurements electrochemical specific capacity: battery shelved change into to 0.2 volt of voltage with 0.2 milliampere of electric current after 60 minutes, then respectively with 1 milliampere, 0.8 milliampere, 0.7 milliampere, 0.6 milliampere constant current discharge to 0.005 volt, after shelving 30 minutes, again with 0.5 milliampere, 0.3 milliampere, 0.1 milliampere, 0.06 milliampere, 0.03 milliampere constant current discharge to 0.005 volt, shelve after 30 minutes with 0.3 milliampere of electric current constant current charge, record charges to cell voltage and reaches 2.5 volts time, according to normal capacity (MAH)=charging current (milliampere) * charging interval of button cell (hour) calculate the normal capacity of button cell, normal capacity promptly gets the electrochemical specific capacity of button cell positive active material (composite material S1) divided by the weight of the positive active material (composite material S1) of button cell, and the result is as shown in table 1.
2, cycle performance
Cycle performance according to following step test compound material S1:
With 6.39 gram LiCoO
2Being positive active material, is barrier film with the modified polypropene barrier film, with the LiPF of 1 mol
6Solution is electrolyte, be negative electrode active material with the composite material S1 that made by the foregoing description 1 and Kynoar with the mixture (2.00 gram) of weight ratio 80:20, makes 043450A type (designing battery capacity is 800 MAHs) secondary lithium battery.
Cycle performance according to following step measurements composite material product S1: with 80 milliamperes of (0.1C) constant current charges 960 minutes, deboost is 4.2 volts, shelved after the charging 15 minutes, with 160 milliamperes of (0.2C) constant current discharge to 3.0 volts, repeat the above-mentioned step 50 time of discharging and recharging, the discharge capacity after the record circulation 50 times is calculated this capacity and the ratio of discharge capacity first, be the capability retention of circulation after 50 times, the result is as shown in table 1.
Embodiment 8-12
Following embodiment is used to illustrate the chemical property of composite material provided by the invention.
According to the discharge first of the method test compound material of embodiment 5 must capacity and 50 circulations after capability retention, different is, the composite material S1 that the foregoing description 1 makes is replaced by the composite material S2-S6 that embodiment 2-6 makes respectively, and the result is as shown in table 1.
Comparative Examples 2
This Comparative Examples is used to illustrate the chemical property of composite material of the prior art.
According to the discharge first of the method test compound material of embodiment 5 must capacity and 50 circulations after capability retention, different is, the composite material S1 that the foregoing description 1 makes is replaced by the reference composite material CS1 that Comparative Examples 1 makes, the result is as shown in table 1.
Table 1
From the result of last table 1 as can be seen, composite material provided by the invention has excellent electrochemical properties, compare with existing composite material, the specific capacity of composite material provided by the invention obviously improves, and significantly improved the cycle performance of the battery that contains composite material of the present invention, illustrated that composite material provided by the invention can improve the cycle performance of specific capacity and the battery that obtains simultaneously.
Claims (11)
1, a kind of composite material, this material contains material with carbon element and has embedding/take off the non-material with carbon element of lithium activity, it is characterized in that described material with carbon element is a carbon nano-tube, with respect to 100 weight portions have an embedding/take off the non-material with carbon element of lithium activity, the content of described carbon nano-tube is the 5-50 weight portion.
2, material according to claim 1, wherein, with respect to 100 weight portions have an embedding/take off the non-material with carbon element of lithium activity, the content of described carbon nano-tube is the 10-30 weight portion.
3, material according to claim 1, wherein, the average tube diameter of described carbon nano-tube is the 20-40 nanometer, length is the 5-15 micron.
4, material according to claim 1, described non-material with carbon element with embedding/take off lithium activity is an elemental silicon; Si oxide SiO
x, 0＜x≤1.5 wherein; Cobaltosic oxide; Di-iron trioxide; In tin oxide and the stannous oxide one or more.
5, the preparation method of the described composite material of claim 1, it is characterized in that, this method comprises carries out ball milling with non-material with carbon element and carbon nano-tube with embedding/take off lithium activity under inert gas atmosphere or vacuum condition, dry then, with respect to 100 weight portions have an embedding/take off the non-material with carbon element of lithium activity, the consumption of described carbon nano-tube is the 5-50 weight portion.
6, method according to claim 5, wherein, with respect to 100 weight portions have an embedding/take off the non-material with carbon element of lithium activity, the consumption of described carbon nano-tube is the 10-30 weight portion.
7, method according to claim 5, wherein, the average tube diameter of described carbon nano-tube is the 20-40 nanometer, length is the 5-15 micron.
8, method according to claim 5, wherein, described non-material with carbon element with embedding/take off lithium activity is an elemental silicon; Si oxide SiO
x, 0＜x≤1.5 wherein; Cobaltosic oxide; Di-iron trioxide; In tin oxide and the stannous oxide one or more.
9, method according to claim 5, wherein, described carbon nano-tube is also carried out acidification before ball milling, the method of described acidification comprise with carbon nano-tube with acid contact, described acid is nitric acid and/or sulfuric acid, and the time of contact is 8-12 hour, and the temperature of contact is 50-90 ℃.
10, a kind of negative pole, this negative pole comprise collector and the negative material that loads on this collector, it is characterized in that described negative material contains any described composite material among the claim 1-4.
11, a kind of lithium battery, this battery comprises pole piece and electrolyte, and described pole piece comprises positive pole, negative pole and the membrane layer between positive pole and negative pole, it is characterized in that, and described negative pole is the described negative pole of claim 10.
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| CN102427129A (en) * | 2011-12-12 | 2012-04-25 | 浙江大学 | Lithium ion battery composite negative electrode material, its preparation method, negative electrode with application of material thereof and lithium ion battery |
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| CN112510180A (en) * | 2020-12-02 | 2021-03-16 | 江苏科技大学 | Silicon oxide-carbon filament active material and preparation method and application thereof |
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